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arXiv · 2511.07580

Seniority-Zero Canonical Transformation Theory: Reducing Truncation Error with Late Truncation

Daniel F. Calero-Osorio·Paul W. Ayers
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Abstract

We show how to add the effects of residual electron correlation to a reference seniority-zero wavefunction by making a unitary transformation of the true electronic Hamiltonian into seniority-zero form. The transformation is treated via the Baker Campbell Hausdorff (BCH) expansion and the seniority-zero structure of the reference is exploited to evaluate the first three commutators exactly; the remaining contributions are handled with a recursive commutator approximation, as is typical in canonical transformation methods. By choosing a seniority-zero reference and using parallel computation, this method is practical for small- to medium-sized systems. Numerical tests show high accuracy, with errors $\sim 10^{-4}$ Hartree.

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Daniel F. Calero-Osorio, Paul W. Ayers. 2025-11-10. Seniority-Zero Canonical Transformation Theory: Reducing Truncation Error with Late Truncation. https://doi.org/10.1021/acs.jctc.5c01892

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